Activator solution for machineless hair-waving pads



Patented Nov. 21, 1950 ACTIVATOR SOLUTION FOR MACHINELESS HAIR-WAVING PADS Harry W. Mace, Glendale, Calif., assignor to Samuel O. Ronk and Louise R. Hunter, both of Burbank, Calif.

No-Drawing, Application January 31, 1948, Serial No. 5,689

' 10 Claims.

This invention relates to the art of perma nent waving and in particular to solut ons suitable for activating heating pads normally used in producing machineless waves.

The object of this invention is to provide an activator solution that will cause the reaction to take place between the chemicals in a conventional water activated machineless heatin pad in the same manner as though the pad were wet with waterb Another object of this invention is to provide a heating pad actvating solution that contains ingredientscapable' of leaving the hair soft and glossy after the solution has ceased to serve as an activator. in effect producing results superior to those obtained by the so-called oil machineless type of wave.

A further object is to prov de an improved activating solution for use with water activated machineless pads containing an oil-like substance that will be deposited on the hair after the water in the mixture has been driven off by the heat generated by the pad and will not be 'easily rinsed from the hair when it is washed after the wave has'been set A conventional heating pad used in producing water activated machineless waves generally comprises a mixture of dry ingredients such as potassium chlorate, finely-divided aluminum, copper carbonate, and aluminum sulphate with or without an inert filler. These ingredients react with each other when-they are moistened with water, producing the heat necessary to wave the hair. Since the waving solutions generally employed are alkaline in nature, while theactive ingredients in the heating pad are acidic in nature, the alkaline waving solution must be prevented from soaking into the heating pad and neutral zing the acidic components making the heating pad useless. This is ordinar ly prevented by placing an applicator pad between the wet surface of the hair and the permeable surface of the machineless heating pad. The

ordinary applicator pad comprises a sheet of water resistng material laminated to a sheet of water-absorbent material. The water-absorbent sheet of the'applicator is moistened and placed in contact with the heating pad envelope.

The water diiiuses through the permeable covering of the heating pad and initiates the reaction between the chemicals. 1

A particular feature of mv invention is that my novel activator solution eliminates the necessit of using an applicator pad having an impermeable sheet to prevent the alkaline ha r waving solution from entering the heating pad The pads in-general usefor giving so-called -i1.machine1ess- Waves (li ter in qinvqs t qn 2 from the type of heating pads activated with water. This type of pad usually consists of a porous envelope in which there is contained a mixture comprising 40% to 60% by weight of potassium permanganate and an inert filler. These pads are activated by so-called oily solut ons which are generally no more than an aqueous solution of glycerol, sorbitol, or ethylene glycol. The alcoholic solution soaks into the pad and when the alcohols come in contact with the permanganate they become oxidized and generate heat. m y

A general objection to the use of this oil machineless type of heating pad is that per manganates in general have a rather high water solubility making the resulting solution highly colored. Thesesolutions may cause injurious stains. if broughtin contact with the hair or fabrics.

,Another disadvantage attending the use of permanganate heating pads and their activator solution isthat the so-called oily portions of the solution, that is, the alcohols, such as glycerol, sorbitol and the ethylene glycols actually impart no lasting body to the hair because they are completely washed away when the hair is rinsed after the waving process is completed.

Another, objection to the use of permanganate heating pads is that the amount of heat developed by the normal size pad is low compared ,to that developed by a water activated heating pad ofequivalent size. Therefore, it would be necessaryto use a much larger heating pad to produce a wave similar to that. obtained with the water machineless pad. Sincethis is impract cal due to limiting dimensions ofthe curlers, the result is that an oil, machineless wave generally produces weaker curls than a water activated machineless wave.

The activator solutions normally used in giving, oil machineless waves cannot be employed to activate a standard water machineless pad because they conta n water soluble organic substances which when dissolved in the water in quantities, sufficient to give it an oily appearance, lower the dielectric properties of water and reduce its solvent power for any highly ion-- "of a novel activating aqueous solution-that is colorless, contains desirable amounts of high -molecular weight organic compounds and can 1 be us'ed'to activate the ordinary water activated mach neless heating. pad... generating approximately the same amount of heat as will be developed if the pad were wet with water.

My novelaqueous solution imparts a lasting gloss and body to the hair even though the high molecular weight organic compound is present in smaller amounts than in the conventional oil activator solution used with permanganate pads. These substances do not easily rinseaway. when the permanent waving solution is washed out of the ha r. the water-activated type and containno-permanganate or other highly colored oxidizing salt, there is no danger of staining and this par ticularly objectionable feature'encountered inthe ordinary o l machineless wave is therefore entirely eliminated.

My novel pad activating solution comprises water .andan organic water-soluble, high molec ular weight,..aliphatic compound capable of. imparting oil properties to the water when dissolved -in it. A suitable accelerator or accelerae tors-mixture isv added to the aqueous solution.

My accelerator or combination of accelerators performs two independent functions; first .it compensates for an inhibit ng -enect of' the dissolved organicv substances, and secondly it protects the heating pad from the injurious-ef-v feet of the alkaline waving solution.

The organic substances that I employ in the preparation of this, padactivating solution cornprise long, strai ht chain ali hatic compounds of .C, H, and having atleast one oxygen-con.- taining po ar .group for every three carbon atoms.

A preferred arrangement is .one .in \vhich..the polar groups are fairlyeven y distributed among from 65%-100% of the carbon atoms in the Since the heating padsernployed are.

chain, that is, one po ar group is present between.

1-3 carbon atoms. This would allow a maximum of..35% ofthe total carbon ato s in the, chain to. be arranged side by side without having any polar grou s between themif necessary, How,-

ever even distribution of. the polar groups tends; toinsure greater water solubility, and therefore compoundshaving such a distributionare more desirable. The substances.selectedshou d be of such anature that they-are not too readily,solu, ble, thus preventing them frombeing.rinsed away when the hair. is subsequently washed-i Furthermore, the substance should not become sticky or tacky at any stage of the evaporation but should in.5% to 20% concentrations impart sufiicient viscosity and give an unctuous. and oily feelto its water solution and to the hair at, alltirnes.

Preferably the material should be .of such a nature that the addition of between 5% to .20% by weight of the substance, based on the, otal weight of the solution will not increase the viscosityof the solution, to a degree where it will not pour easily and cannot penetrate .the machineless. heating padsfreely, v v

- A. preferred group .of organic compounds that fill. the above. requirements comprises the high molecular weight ethylene oxide polymers commonly referred to as polyethylene glycols and also called polyoxyethylene glycols. These substances have a general formula om onion din mats could also be used if it otherwise meets the above viscosity requirement and is sufiiciently soluble inw,ater....

Other representatives of the broad group of organic compounds that fulfill the broad definition for the organic compound are the water soluble polypropylene glycols having molecular weights ranging between about 500 and about 6000 and polyvinyl alcohols preferably of low" viscosity, and containing less than 15% unhydrolyzed vinyl acetate groups. Since the molecular weightsrof the polyvinyl alcohols are difficultto determinewith accuracy it is more convenient to use the viscosity in centipoises of a 4% by weight aqueous solution at 20 C., as determined with a Hoeppler viscosimeter, as a means for designating the type of polyvinyl alcoholused; The viscosity of .the polyvinyl'alcohols suitable. for use? in compounding my. invention ranges frombetween-aboutl and about 25.;centipoises at the above conditions; i v

Aliphatic alcohol ethers; of the polymers...mentioned. above that possess the required water solubi1ity. may.. also beemployed. How-ever, .compounds that hydrolyze in mild acid solution can not be. used The speed with which a water activated machineless pad generates heat is generally dependentupon the rate-of solution of the accelerator therein. For this reason the-proper selection of the acceleratingv material to be added to the solution isquite important.

Accelerators may. be broadly divided into two groups:

One group of materials that isTsuitable for'accelerators. is the water soluble inorganic acid salts of cations whichwi l precipitate: in alkaline solution. The acid radical should furthermore be one capable of reacting with aluminum.

A second group of materials that may also be used are the water soluble salts of inorganic acids such as HCl and H2804 capable of reacting'w'ith aluminum; strong water soluble organic acids capable of reacting with aluminum, water soluble aliphaticamine salts of inorganic acids as well as'their derivatives capable of reacting with Al, as well as free inorganic acids capable o f';r eacting with Al. Certain of these amine hydrochlorides maybe classified functionally in group one, dependng upon the properties. of the free amine. .,The pH of a normal-aqueous solution of. the accelerator should be below about5.0. f

. At-least one accelerator from the first group should be present in order to protect the heats. Dad fromth ka in wavin solution an if further accelerationis' desired one or more of the accelerators in group two .can be added.

Examples of the strongly acidic water soluble inorganic. salts are aluminum chloride, aluminum sulphate, amino'nium' chloride and ammonium sulphate. i V

Examples of thestrongorganic acids are citric acid,tar taric acid, lactic acid and other. acids ofsimilar strength.

Examples of the water soluble amine hydrochlorides are diethylhexylamine hydrochloride, l-hydroxyethyl 2 heptadecynylglyoxalidine hydrochloride and similar amine hydrochlorides. .iThe preferred accelerator because. of its cheapness availability and' excellent performance'is amixture-of aluminum chloride and ammonium chloridein percentages varying. betweenand 7% by weight. of ammonium chloride based on the Weight of the total aqueous solution. and

Ethylene accuses 2 by weight aluminum chloride based on the weight of the-total aqueous solution. v

The incorporation of an additional percentage of an acid-forming salt or other substance into the aqueous activator solution proves beneficial in overcoming any retarding efiect caused by the addition of organic compounds to the solution. This may be explained when it is seen that the initiating action of a water activated heating pad occurs in two stages: First the aluminum sulfate is dissolved by the water, and secondly the aluminum sulfate solution formed reacts with the copper carbonate in the pad forming a salt. The presence of any dissolved organic compound tends to lower the rate of solution of the aluminum sulfate,therefore, the time required for the first stage would beincreased considerably. The addition of an accelerator such as those described to the solution compensates for this slowing down action by providing a solution that reacts directly on the copper carbonate:

The use of applicators provided with impermeable layers is not desirable when an organic substance that can impart oily properties to the water is used in theactivating solution because the impermeable sheet prevents the organic substances from coming in contact with the hair.

Up to the present time the use of a permeable applicator pad has been impractical since the highly alkaline waving solution would quickly penetrate the pad and neutralize the acidic constituents destroying their effectiveness. My novel activating aqueous solution may be used in conjunction with a porous applicator pad since it contains metal salts capable of precipitating insoluble hydroxides such as aluminum hydroxide when the acid metal salt is neutralized by the alkaline waving solution. The metal hydroxide is deposited as an insoluble gelatinous film on the side of the a plicator through which the alkaline waving solution must pass thus effectively preventing the alkaline waving solution from reaching the heating pad. at the same time allowing a substantial portion of the organic compounds in the activator solution to be ,deposited on the hair. I V

Other compounds that will also serve satisfactorily are colorless acid salts of metals capable of precipitating insoluble hydroxides and releasing acid radicals that will react with the aluminum in the pad. Examples are the salts of magnesium, aluminum, zinc, and titanium such as the chlorides and sulfates.

Another group of chemical compounds that may be also used to prevent the passage of the alkaline waving solution are the water soluble aliphaticamine hydrochlorides and their derivatives which precipitate insoluble free amine when neutralized by the alkaline solutions, Examples of the last-named group of substances are diethylhexylamine hydrochloride, l-hydroxyethyl 2 heptadecynylglyoxalidine hydrochlorides and similar aliphatic amine hydrochlorides.

The activator solution according to my invention may be broadly compounded within the following approximate limits:

Per cent oxide polymers (polyoxyethylene glycols, or equivalent) (average molecular weight range between 1000 and 7000) 5 Ammonium chloride 1 /2- 8 Aluminum chloride 2 /2-10 Water M About 60 -90 A preferred form of the solution 'is as follows:

Per cent by weight Ethylene oxide polymer (polyoxyethylene glycol-average molecular weight 6000) 10.

Ammonium chloride 3 Aluminum chloride ,4 Water 83 7 Another preferred form of the invention is as follows:

I Per cent by weight Ethylene oxide polymer 4000 average molecu- On a water free basis the organic material is present in amounts varying between about 30% and about by weight based on the weight of the non-aqueous ingredients. The water soluble acidic constituent is present in amountsvarying between about 20% and about 50% by weight based on the weight of the non-aqueous ingredients therefore in the above formulations the A1013 will be from about 10% to about 50% by weight of the non-aqueous ingredients and the NH4C1 will vary between 1% and 20% by weight of the non-aqueous ingredients.

While it has been stated that the average molecular weight of the preferred ethylene oxide polymer ranges between 1000 and 7000 'it is contemplated to include within the scope of this invention allied materials having molecular weights exceeding 7000 as long as the materiahis sufliciently water soluble and is not sticky or tacky when dry. The higher molecular weight ethylene oxide polymers may also have incorporated therein small quantities of lower molecular weight poly thyleneglycols as long as the amount of such substance used does not lower the average molecular weight below 1000. The preferred ethylene oxide polymers that have been genera ly used are those having average molecular weights of approximately 1500, 4000 and 6000 average molecular weight.

My novel solution possesses the advantagethat it is pos ible to employ the more effective water machineless heating pads with an activator solution containing oily materials capable of imparting desirable properties to the hair without losing any of the heat thus insuring a more satisfactory permanent wave.

Another advantage of my solution is that it permits the use of permeable applicator pads which al ow-'asubstantial portion of the organic materials in the solution to become deposited on the hair. yet at the same time prevent diffusion of any of the alkaline waving solution from the hair into the heating pad.

My novel activator solution contains organic substances that impart a lasting gloss and softness to the hair and are not rinsed away on the first washing.

A further advantage of my invention is that the desirable efiect of an oil machineless wave can be obtained without the danger of staining I claim:

1. An activator solution for use with a normall water-activated machineless hair waving pad, said solution comprising polyoxyethylene glycol havingiah averag e molecular weight ranging between about 1000 and about 7000 in -an amount ranging between about and about 20% bywei'ght based on the weight of the total solution, ammonium chloride in an amount varying'between about' /g% to about 8% 'byiwei'ght basedo'n" the weight of the total solution, aluminuin chloride in 'an amount varying between about 2 to about by weight based on the w'eighti-oi 'the' total solution and water in an amount varying between about 60% and about 90% by weight based on the weight of the total solution.

2. An'ac'tivator solution for use with a normally water-activated hair -waving pad, said sotundra"compnsingabout I1 by weight polyoxy thylene"glycol having an average molecular weight of '4000'jab6ut 3%by weight of ammonium chloride,-about--4% by weight A1013, and about"82% by weight water. e

3. An activator composition for usewith a water activated-"machineless 'hair waving Y pad comprising: a water-solubleorga-nic material selected from the group consisting of polyoxyethylene glycols'having a molecular weight above 1000;''polypropy1ene glycols having molecular weights abovg500ypolyvinyl alcohols containing less than unhydrolyzed vinyl acetate groups, an "aqueous solution of said polyvinyl alcohols containing 4% by weight having an average viscosity at C." of between about 1 and about centipoises determined by a Hoeppler "viscosimeter; and*iiliphatic alcohol-ethers of said polymers: between about 10% and about 50% by weight; basedon the weight of the total 'nonaqueous ingredients-bf-AlCli: andbetween 0% arid-about 20% by weight, based'on' the weight of the total non-aqueous ingredients of an acidic constituent-selected from the group consisting OfHCL'I-IzSOi, water-soluble salts of H01: watersolubl'esalts of H2604, and water-soluble organic acids, an aque'ous'solution of 'said' acidic constituent,-when"containing one chemical equivalent per liter,-having a pH below about5.0.

activator composition according to claim 3 wherein said water soluble'orga'nic material is present in the proportion between about and about'80% 'by weight, based on the weight of the total'non-aqueous ingredients.

' 5 An activator compositionaccording'to claim 3 whereih'between about 60% and about 90% by weight of water, based On the total weight of the solution is added to the non-aqueou's ingredients. 6. In machineless hair waving the combination comprising the activator composition of claimfi and'a heating pad comprising a mixture 'o'fAl, CuCOs. A12(SO4)3, and K0103.

7-. An activator composition for use with a water activated machineless hair waving pad, said composition containingi a water soluble org'anic material selected from the group consisting of polyoXyethylene glycols having molecular -weights above 1000; polypropylene glycols' having a molecular weight above 500; polyvinyl alcohols containing less than 15% unhydrolyzed vinyl acetate groups, an aqueous solution'of said polyvinyl alcohols containing 4% by weight having an average viscosity-at 20 C. of between about 1 and about 25 centipoises determined by a Hoeppler viscosimeter; and aliphatic alcohol ethers of 8: said polymers 5 said composition also containing between-about 10% and about by-weight of, A1613; based on theweight of the nonvaqueous ingredients: said'composition further containing between about-1% andabout 30% by weight of tivating solution AlCh, and precipitating;a layer of ARCH): on said-applicator-pad when said waving solution comes in contact with said-A1013.- 9: In a hair treating process employinganlape plic'ator pad, a water: activated I machineless :hair

Lil)

waving heating pad, and an activating solution, the method of preventing passage of'an alkaline waving solution through-said applicatorspad into said a heating pad which" comprises incorporating insaid activating'solution a compoundlselected from the group consisting of AlGlz,-MgCla,.ZnGlz-, TiCh, A12(SO4')3, MgSO4, and ZnSOi, andprecipitating an insoluble-layer on. said applicator pad when said alkaline waving solution comes in- :contact-with said compound;

10.. An activator-composition. for use with a water-activated machineless hair. waving pad comprising a water-solubleorganic material selected from the-group. consisting of .polyoxyethylene glycols having amolecular weight above 1000;- polypropylene glycols having. molecular weights above 500; polyvinyl alcoholscontaining less than 15% unhydrolyzed vinyl acetate groups, an aqueous solution of said polyvinyl alcohols containing 4% by weight having an average viscosity .at-20'C. of between about 1 and.-about.25 centipoises determined by a .Hoeppler viscosirn-- eter; and aliphatic alcohol ethers-0f said. poly,- mers: between about 10% and. about 5.0%v by weight, based on the weightof .thetotal non-v aqueous ingredients, of a compound selected from the group consisting of AlCls, M'gClz, ZnCIaJIiCh, A12(SO4)3, MgSO4 and 2118041 and between 0% and about 20% by weight, based on the weight of the total non-aqueous ingredients of an acidic constituent selected from thegroup consisting of HCl, Hzsoawater soluble salts of I-ICLwater. soluble salts of H2304, and water soluble organic acids, an aqueous solution of said acidic constituent, when containing one chemical equivalent per liter, having a pH below about 5.0.

HARRY W. MACE.

REFERENCES CITED The following references. are of record in the file of this patent: 

1. AN ACTIVATOR SOLUTION FOR USE WITH A NORMALLY WATER-ACTIVATED MACHINELESS HAIR WAVING PAD, SAID SOLUTION COMPRISING A POLYXYETHYLENE GLYCOL HAVING AN AVERAGE MOLECULAR WEIGHT RANGING BETWEEN ABOUT 1000 AND ABOUT 7000 IN AN AMOUNT RANGING BETWEEN ABOUT 5% AND ABOUT 20% BY WEIGHT BASED ON THE WEIGHT OF THE TOTAL SOLUTION, AMMONIUM CHLORIDE IN AN AMOUNT VARYING BETWEEN ABOUT 1/2% TO ABOUT 8% BY WEIGHT BASED ON THE WEIGHT OF THE TOTAL SOLUTION, ALUMINUM CHLORIDE IN AN AMOUNT VARYING BETWEEN ABOUT 2 1/2% TO ABOUT 10% BY WEIGHT BASED ON THE WEIGHT OF THE TOTAL SOLUTION AND WATER IN AN AMOUNT VARYING BETWEEN ABOUT 60% AND ABOUT 90% BY WEIGHT BASED ON THE WEIGHT OF THE TOTAL SOLUTION. 